CN109279916A - A kind of preparation method and plated film anti-bacteria ceramic of plated film anti-bacteria ceramic - Google Patents
A kind of preparation method and plated film anti-bacteria ceramic of plated film anti-bacteria ceramic Download PDFInfo
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- CN109279916A CN109279916A CN201811210767.1A CN201811210767A CN109279916A CN 109279916 A CN109279916 A CN 109279916A CN 201811210767 A CN201811210767 A CN 201811210767A CN 109279916 A CN109279916 A CN 109279916A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
Abstract
The present invention provides a kind of preparation method of plated film anti-bacteria ceramic, and colloidal sol uniformly dense is coated to by pretreated ceramic tile print with self-control ultrasonic spray apparatus.Colloidal sol is atomized into fine droplets particles by effect of the present invention using industrial atomising head in ultrasonic wave, forms aerosol with gas mixing.Fine and closely woven droplets particles are transported to reaction chamber under the gas pressure of air pump, form thin film coated on potsherd, further pyrolysis film forming.It makes a search to the anti-bacteria ceramic of surface coating to the anti-microbial property of Escherichia coli (ATCC 25922), staphylococcus aureus (ATCC 6538) and Candida albicans (ATCC 10231), according to plated film height, coating layers, plated film time and the maturing temperature in the titanium dioxide nano material colloidal sol of sample situation change metal ion mixing during the preparation process doping and doping molar ratio, the type of surfactant and anti-bacteria ceramic preparation process.
Description
Technical field
The present invention relates to field of novel, and in particular to a kind of preparation method and plated film antibacterial pottery of plated film anti-bacteria ceramic
Porcelain.
Background technique
TiO2Have that nontoxic, inexpensive, chemical property is stable, photocatalytic activity is high, antibacterial etc. as photochemical catalyst
Advantage is always the emphasis of people's research, is usually used in preparing plated film anti-bacteria ceramic, i.e. TiO2Film is covered on ceramic surface and is made
Anti-bacteria ceramic.But TiO2It is not without disadvantage, since its forbidden bandwidth (3.0eV-3.2eV) is wider, ultraviolet light can only be absorbed, and
Ultraviolet light only accounts for the 4% of sunlight, and TiO2After black light irradiation, quantum yield is low, and not more than 10%；Together
When its generation that is stimulated electrons and holes recombination rate it is higher.These factors all strongly limit TiO2Photocatalysis efficiency.It wants
Want to solve these problems and just need to TiO2It is doped modification, to improve photocatalytic activity.
For TiO2Modification, have three ways, such as metal-doped, nonmetal doping and codope.The main body of chanza
Present two aspects: first is that the photo-generated carrier generated to intrinsic excitation plays the role of capturing trap；Second is that one can be generated
A impurity energy level is to TiO2Conduction band and valence band between, and participate in photoactivation process.Metal-doped common metal ion is main
There is Cu2+、Fe3+Plasma doping and Th4+、Ce3+、Er3+、Pr3+、Gd3+、Nd3+、Sm3+Etc. rare earth ion doped.Nonmetallic ion
Doping mainly has C, N, S etc..According to XRD and DRS, analysis shows, codope preferably inhibits grain growth, improves crystal phase
Transition temperature.
The preparation method of plated film anti-bacteria ceramic, include electrophoresis, chemical vapour deposition technique (CVD), dip-coating method,
Physical vaporous deposition (PVD) etc..Wherein TiO is prepared using electrophoresis2Film can by membrance current and film formation time come
Control the thickness of film, obtained TiO2Film has high-flatness and high roughness.Applied Electrochemistry method prepares TiO2It is thin
Film, it is also desirable to film is heat-treated, disadvantage is must to be film-made in conductive substrates.Chemical vapour deposition technique (CVD)
Substantially a kind of gaseous substance is at high temperature by chemically reacting the film forming side for generating solid matter and being deposited on substrate
Method.Dip-coating method is that the substrate that will be cleaned immerses among colloidal sol well prepared in advance, pull rate is then accurately controlled, by base
Plate is steadily evenly lifted from colloidal sol and is come out, and forms one layer of uniform liquid film in substrate surface under viscosity and gravity,
And then solvent evaporates rapidly, is attached to the colloidal sol rapid gellation of substrate surface and forms layer of gel film.But dipping mentions
Daraf(reciprocal of farad) is not easy to control, high to viscosity requirement, is affected by gravity greatly.Physical vaporous deposition (PVD) is to prepare hard coating
The common technology of (dura mater) can prepare the high quality TiO with high index2Film, process stabilizing is easily controllable, energy
It is enough applied in the large-scale production such as building glass but this method must carry out under vacuum conditions and device therefor price is high
It is high.These above-mentioned methods are all to have formd TiO in plated film2Or doping vario-property TiO2Film.
That there are production equipments is high for the prior art, and working condition harshness is not easy to realize, the anti-bacteria ceramic quality of production is bad,
TiO2The disadvantages of antibacterial film and poor ceramic junction resultant force.
Summary of the invention
(1) technical problems to be solved
To problem of the existing technology, the present invention provides a kind of preparation method of plated film anti-bacteria ceramic, makes TiO2Film
Uniform and adhesion-tight, it is applied widely, it is cheap, Metal Ions Co-doped modifying titanium dioxide is coated with particularly suitable for surface
The preparation of the anti-bacteria ceramic of film.
(2) technical solution
In order to achieve the above object, the present invention provides a kind of preparation method of plated film anti-bacteria ceramic comprising following steps:
S1, it prepares doping vario-property colloidal sol: soluble titanium hydrochlorate, surfactant, at least one being added in a solvent and is used for
Doping vario-property colloidal sol is made under chelating agent existence condition in the metal ion compound of doping；
S2, the doping vario-property colloidal sol is sprayed into ceramic surface: using supersonic spraying, doping prepared by step S1
Modification sol sprays to ceramic surface, forms the doping vario-property sol pellicle of even compact；By the ceramic surface temperature when spraying
Degree control is at 50~70 DEG C；
The surface: being covered with the ceramics of doping vario-property sol pellicle by S3, calcination process, at high temperature aerobic roasting, system
Metallic ion-doping modification TTiO must be coated with2The anti-bacteria ceramic of film.
Further, the soluble titanium hydrochlorate that step S1 step is added is butyl titanate.
Further, the metal ion compound that step S1 is added is lithium acetate, zinc nitrate, at least one in cobalt nitrate
Kind.
Further, the surfactant that step S1 is added is neopelex, lauryl sodium sulfate, 12
One of sodium alkyl sulfonate, Polyethylene glycol-2000 and cetyl trimethylammonium bromide.
Further, step S1 be made titanate in doping vario-property colloidal sol, dehydrated alcohol, glacial acetic acid and water volume ratio be
1:14:4:1。
Further, when the doping vario-property colloidal sol is sprayed to ceramic surface by step S2 plated film height be 3cm-15cm,
Every layer of plated film time is 30-90min, coating layers are 1-4 layers.
Further, ceramics will dry 30-60min to step S2 between plated film twice, dry 5-10 hours after all plate
Drying temperature be 90~105 DEG C, drying time be 12~for 24 hours.
Further, stoving temperature from room temperature is warming up to 400-800 DEG C with the rate of 4 DEG C/min when step S3 calcination process
Afterwards, heat preservation roasting 1-5 hours.
Further, potsherd used in step S2 is the conventional ceramic piece for not plating glaze paint, and with deionized water, dehydrated alcohol
It is cleaned by ultrasonic 2 hours with acetone.
It the present invention also provides a kind of plated film anti-bacteria ceramic, is made according to above-mentioned preparation method.
(3) beneficial effect
The principle of preparation method of the present invention is to be atomized into colloidal sol under the action of ultrasonic wave using industrial atomising head fine
Droplets particles, with gas mixing formed aerosol；Then fine and closely woven droplets particles are passed through height under the gas pressure of air pump
Body of calming the anger is transported to reaction chamber, is sprayed on print, and aerosol forms thin film coated on potsherd, and the sol pellicle of formation is
Metal-doped modified TiO2Presoma, then be fired processing, on the one hand make metal-doped modified TiO2Oxidation of precursor sintering
At the metal-doped modified TiO with antibacterial action2, another aspect sintering processes make metal-doped modified TiO2Antibacterial film with
Potsherd is combined closely integrally, and the durability of plated film anti-bacteria ceramic is improved.
The ultrasonic spray pyrolysis device that the present invention uses, the device are very big to the material scope of application, without materials conductive, behaviour
It is lower to make equipment cost, which is industrial ultrasonic atomizer, easy industrialization promotion, suitable material range
Extensively.Granularity fine and even after atomization, larger atomized drop stays in surge chamber after surge chamber, is atomized fine particle with gas
Pump gas enters spray equipment, since atomizing particle is subtle, easily penetrates into potsherd, the spraying on potsherd surface is more evenly
Securely, the later period is impregnated by sewage and the detection modes such as rain drop erosion test to the fastness of its plated film, carries out nothing
Water impregnates and the antibiotic rate of the anti-bacteria ceramic of rain drop erosion remains to reach the 90% of former antibiotic rate.
Detailed description of the invention
Fig. 1 is ultrasonic spray pyrolysis coating apparatus process flow chart of the invention；
Fig. 2 is the XRD diagram of the cobalt nitrate doped titanium dioxide nano material of the different dopings of 1-6 of the embodiment of the present invention
Spectrum；
Fig. 3 is the UV-Vis- of the cobalt nitrate doped titanium dioxide nano material of the different dopings of 1-6 of the embodiment of the present invention
DRS map；
Fig. 4 is the FT-IR figure of the cobalt nitrate doped titanium dioxide nano material of the different dopings of 1-6 of the embodiment of the present invention
Spectrum；
Fig. 5 is the antibacterial ring size of the cobalt nitrate doped titanium dioxide nano material of the different dopings of 1-6 of the embodiment of the present invention
Figure；
Fig. 6 is the cobalt nitrate doped titanium dioxide nano material of the different dopings of 1-6 of the embodiment of the present invention to large intestine bar
The anti-microbial property of bacterium influences；
Fig. 7 is the XRD analysis figure of zinc/lithium doping TiO 2 sol nano material of the embodiment of the present invention 7；
Fig. 8 is the sem analysis figure of zinc/lithium doping TiO 2 sol nano material of the embodiment of the present invention 7；
Fig. 9 is the UV-Vis-DRS analysis of zinc/lithium doping TiO 2 sol nano material of the embodiment of the present invention 7
Figure；
Figure 10 is the FT-IR map of zinc/lithium doping TiO 2 sol nano material of the embodiment of the present invention 7；
Figure 11 is the antibacterial ring size figure of zinc/lithium doping TiO 2 sol nano material of the embodiment of the present invention 7；
Figure 12 is the XRD analysis figure of cobalt/zinc doping TiO 2 sol nano material of the embodiment of the present invention 8；
Figure 13 is the sem analysis figure of cobalt/zinc doping TiO 2 sol nano material of the embodiment of the present invention 8；
Figure 14 is the UV-Vis-DRS analysis of cobalt/zinc doping TiO 2 sol nano material of the embodiment of the present invention 8
Figure；
Figure 15 is the FT-IR map of cobalt/zinc doping TiO 2 sol nano material of the embodiment of the present invention 8；
Figure 16 is the antibacterial ring size figure of cobalt/zinc doping TiO 2 sol nano material of the embodiment of the present invention 8；
Figure 17 is the cobalt doped titanium dioxide nano material of the different surfaces activating agent of 9-13 of the embodiment of the present invention to large intestine
The anti-microbial property of bacillus influences；
Figure 18 is the nano material of the cobalt doped TiO 2 sol of the different surfaces activating agent of 9-13 of the embodiment of the present invention
Antibacterial ring size figure；
Figure 19 is the cobalt doped titanium dioxide nano material anti-bacteria ceramic of the different plated film height of 14-18 of the embodiment of the present invention
The anti-microbial property of Escherichia coli is influenced；
The XRD spectrum of the plated film height that Figure 20 is 14-18 of embodiment of the present invention anti-bacteria ceramic prepared when being 8cm；
The SEM spectrum of the plated film height that Figure 21 is 14-18 of embodiment of the present invention anti-bacteria ceramic prepared when being 8cm；
Figure 22 is the cobalt doped titanium dioxide nano material anti-bacteria ceramic of the different coating layers of 19-21 of the embodiment of the present invention
The anti-microbial property of Escherichia coli is influenced；
The XRD spectrum of Figure 23 is the coating layers of 19-21 of embodiment of the present invention anti-bacteria ceramic prepared when being 2 layers；
The SEM spectrum of Figure 24 is the coating layers of 19-21 of embodiment of the present invention anti-bacteria ceramic prepared when being 2 layers；
Figure 25 is the cobalt doped titanium dioxide nano material anti-bacteria ceramic of the different plated film times of 22-25 of the embodiment of the present invention
The anti-microbial property of Escherichia coli is influenced；
The XRD diagram of Figure 26 is the plated film time of 22-25 of embodiment of the present invention anti-bacteria ceramic prepared when being 45min
Spectrum；
The SEM figure of Figure 27 is the plated film time of 22-25 of embodiment of the present invention anti-bacteria ceramic prepared when being 45min
Spectrum；
Figure 28 is the cobalt doped titanium dioxide nano material anti-bacteria ceramic of the different maturing temperatures of 26-30 of the embodiment of the present invention
XRD spectrum；
Figure 29 is the cobalt doped titanium dioxide nano material anti-bacteria ceramic of the different maturing temperatures of 26-30 of the embodiment of the present invention
SEM spectrum；
Figure 30 is the cobalt doped titanium dioxide nano material anti-bacteria ceramic of the different maturing temperatures of 26-30 of the embodiment of the present invention
The anti-microbial property of Escherichia coli is influenced.
[description of symbols]
1, air pump compresses air；2, atomized drop；3, ultrasonic atomizer；4, titania solution；5, surge chamber；6, tail gas
Processing unit；7, the potsherd of non-glazing；8, ceramic bases liner；9, heating device.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair
It is bright to be described in detail.The characteristics of ultrasonic spray pyrolysis is that atomizing particle is subtle, and coating is deeply and uniform, and has price low
Honest and clean, the advantages that controllability is high, it can be used for industrialized production.The present invention proposes a kind of preparation method of plated film anti-bacteria ceramic,
The following steps are included:
S1, it prepares doping vario-property colloidal sol: soluble titanium hydrochlorate, surfactant, at least one being added in a solvent and is used for
Doping vario-property colloidal sol is made under chelating agent existence condition in the metal ion compound of doping；
S2, the doping vario-property colloidal sol is sprayed into ceramic surface: using supersonic spraying, doping prepared by step S1
Modification sol sprays to ceramic surface, forms the doping vario-property sol pellicle of even compact；By the ceramic surface temperature when spraying
Degree control is at 50~70 DEG C；
The surface: being covered with the ceramics of doping vario-property sol pellicle by S3, calcination process, at high temperature aerobic roasting, system
Metallic ion-doping modification TiO must be coated with2The anti-bacteria ceramic of film.
Wherein, the soluble titanium hydrochlorate that step S1 step is added is butyl titanate or isopropyl titanate.
Wherein, the metal ion compound that step S1 is added is at least one of lithium acetate, zinc nitrate, cobalt nitrate.
Wherein, the surfactant that step S1 is added is neopelex, lauryl sodium sulfate, dodecyl
One of sodium sulfonate, Polyethylene glycol-2000 and cetyl trimethylammonium bromide.
Wherein, the volume ratio that titanate in doping vario-property colloidal sol, dehydrated alcohol, glacial acetic acid and water is made in step S1 is 1:
14:4:1。
Wherein, plated film height is 3cm-15cm, every layer when the doping vario-property colloidal sol is sprayed to ceramic surface by step S2
Plated film time is 30-90min, coating layers are 1-4 layers.
Wherein, ceramics will dry 30-60min to step S2 between plated film twice, drying drying in 5-10 hours after all plate
Temperature be 90~105 DEG C, drying time be 12~for 24 hours.
Wherein, after stoving temperature is warming up to 400-800 DEG C with the rate of 4 DEG C/min from room temperature when step S3 calcination process,
Heat preservation roasting 1-5 hours.
Wherein, potsherd used in step S2 is the conventional ceramic piece for not plating glaze paint, and with deionized water, dehydrated alcohol and third
Ketone is cleaned by ultrasonic 2 hours.
The metal ion mixing TiO prepared by supersonic spraying2Nano material prepares anti-bacteria ceramic and remains titanium dioxide
Advantage in terms of titanium photocatalysis antibacterial agent chemical property itself, and be doped with new constituent element element and modification is doped to it.Gold
Belong to ion list and is entrained in TiO2Impurity energy level, i.e. TiO are introduced in energy gap2Valence band and metal ion 4f electric layer between have occurred
Migration generates capture energy level, forbidden bandwidth is reduced, to increase metal ion mixing TiO2Nano material is to visible light
It absorbs.Furthermore metal ion mixing can cause TiO2The variation of level structure can both receive TiO2Excitation electricity in valence band
Son, photon, which also can be absorbed, makes electron transition to TiO2Conduction band on and TiO2 is compound that its ABSORPTION EDGE can be made to slightly have institute's red shift, it is right
The influx and translocation of visible region.
Currently, the evaluation criterion of domestic unified inorganic antiseptic service check not yet, in order to inquire into through ullrasonic spraying
The metal ion mixing TiO of method preparation2Nano material anti-bacteria ceramic, the present invention was according to Ministry of Health of the People's Republic of China 2006
Nano material and debita spissitudo thallus are passed through in a liquid using oscillation flask method and are vibrated for a long time by disinfection technology standard, are increased
Contact of the microorganism with anti-biotic material is added to detect its antibacterial action.The bacterium of the present invention reference food and health and epidemic prevention department
The method of inspection, using the qualitative evaluation of the antibacterial around-France anti-microbial property for carrying out Escherichia coli to made sample.Concrete condition such as with
Lower embodiment:
Embodiment 1
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.001mol cobalt nitrate is added, and 0.25g dodecyl is added
Benzene sulfonic acid sodium salt is uniformly dissolved as surfactant, stirring to powder, forms solution B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
S2, ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, with de-
Rouge cotton rub is done spare；
Colloidal sol is poured into ultrasonic spray pyrolysis device, places ceramics on the heating by pretreated ceramic tile print
In base substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 45min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 3cm
It plates to be put into baking oven after a tunic and dry in journey and plates within 30-60 minute the second layer again, all plate drying 5-10 hours afterwards.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 600 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
Embodiment 2-6
The step of with embodiment 1, is similar, and embodiment 2-6 is only the metal ion compound type in set-up procedure S1 and to mix
Miscellaneous amount realizes that remaining condition is constant.Specifically, nitric acid Co doping amounts in embodiment 2,3,4,5,6 be 0.002mol,
0.004mol、0.006mol、0.008mol、0.01mol、
1-6 in conjunction with the embodiments, to embodiment 1-6 preparation cobalt doped TiO 2 sol nano material carry out XRD,
The test such as UV-Vis-DRS, FT-IR, each test result difference are as in Figure 2-4.Embodiment 1-6 is passed through into sol-gel legal system
The nano material of standby cobalt doped TiO 2 sol by oscillation flask method and the antibacterial around-France anti-microbial property to Escherichia coli into
Row test, test result is as follows Fig. 5, shown in 6.
In conjunction with Fig. 2-6, make a concrete analysis of as follows: the nano material of cobalt doped TiO 2 sol is shown in Fig. 2 a-f
XRD analysis figure.As can be seen from Figure 2, with the increase of doping, CoTiO3Characteristic diffraction peak intensity gradually increase, 2 θ=
Detitanium-ore-type TiO at 25.3 (101)2The trend of first increases and then decreases is presented in feature peak intensity, illustrates that the incorporation of appropriate Co can
To inhibit growing up and crystallizing more intact for crystal grain in sample roasting process.Cobalt doped TiO 2 sol is shown in Fig. 3
The UV-Vis-DRS analysis chart of nano material.From figure 3, it can be seen that the TiO of cobalt doped2Nano material ABSORPTION EDGE is obviously to length
Wave direction is mobile, wherein the absorbance with 0.001mol, 0.002mol and 0.004mol is preferable, illustrates that its photocatalysis performance obtains
Raising is arrived.Fig. 4 is the FT-IR map of different doping cobalt nitrate doped titanium dioxide nano materials.As shown in Figure 4, own
Contain the vibration absorption peak of O-H, C-O-C and C-H in the FT-IR spectrogram of material.
Fig. 5 a-f is the antibacterial ring size figure of different doping cobalt nitrate doped titanium dioxide nano materials.It can from Fig. 5
Out, occur Clear & Transparent antibacterial ring size around the sample of different dopings, and the antibacterial ring size size of different dopings is close,
Anti-microbial property is good.Fig. 6 is anti-microbial property of the different doping cobalt nitrate doped titanium dioxide nano materials to Escherichia coli
It influences.From Fig. 6, it is apparent that the different pairs of TiO of nitric acid Co doping amounts2Nano material is to the sterilizing rate of Escherichia coli
With the increase of doping, sterilizing rate fluctuations.Wherein, the highest doping of sterilizing rate is 0.002mol, to Escherichia coli
Sterilizing rate reached 99.6%.
Embodiment 7
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.02mol lithium acetate and 0.004mol zinc nitrate molar ratio is added
For 5:1, and 0.25g neopelex is added as surfactant, stirring to powder is uniformly dissolved, and forms solution B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
S2, ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, with de-
Rouge cotton rub is done spare；
Colloidal sol is poured into ultrasonic spray pyrolysis device, places ceramics on the heating by pretreated ceramic tile print
In base substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 45min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 3cm
It plates to be put into baking oven after a tunic and dry in journey and plates within 30-60 minute the second layer again, all plate drying 5-10 hours afterwards.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 600 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
To embodiment 7 prepare zinc/lithium doping TiO 2 sol nano material carry out XRD, SEM, UV-Vis-DRS,
The test such as FT-IR, each test result difference is as is seen in figs 7-10.Embodiment 7 is prepared into zinc/lithium doping by sol-gel method
The nano material of TiO 2 sol is tested by oscillation flask method and the antibacterial around-France anti-microbial property to Escherichia coli, is surveyed
Test result is illustrated in fig. 11 shown below.
In conjunction with Fig. 7-10, make a concrete analysis of as follows: Fig. 7 is the XRD analysis of zinc/lithium doping TiO 2 sol nano material
Figure.As can be seen, Zn/Li codope TiO2Nano material has expanded TiO2Absorption spectrum, make absorption band red shift, in visible light
There is higher absorbance in range, significantly improves TiO2Photocatalytic activity under visible light.This illustrates that adulterating Zn/Li can make
TiO2Red shift occurs for ABSORPTION EDGE, causes TiO2Band gap narrow, more carriers can be generated under visible light action, to mention
High TiO2Optical response range.Fig. 8 is the sem analysis figure of zinc/lithium doping TiO 2 sol nano material.As schemed
Show, which is made of many fine particles and aggregate, particle uniform doping.Fig. 9 is that zinc/lithium doping titanium dioxide is molten
The UV-Vis-DRS analysis chart of the nano material of glue.It can be seen from the figure that Zn/Li codope TiO2Nano material is expanded
TiO2Absorption spectrum, make absorption band red shift, have higher absorbance in visible-range, significantly improve TiO2Visible
Photocatalytic activity under light.Figure 10 is the FT-IR map of zinc/lithium doping TiO 2 sol nano material.As shown,
Zn/Li codope TiO2Contain the vibration absorption peak of O-H, C-O-C and C-H in the FT-IR spectrogram of nano material.The material
O-H stretching vibration peak in material is conducive to generate more hydroxyl free radicals, improves light-catalyzed reaction activity.
Figure 11 is the antibacterial ring size figure of zinc/lithium doping TiO 2 sol nano material.As can be seen from Figure, around sample
There is Clear & Transparent antibacterial ring size, anti-microbial property is good.Lithium acetate and zinc nitrate molar ratio are the nano material of 5:1 to big
The sterilizing rate of enterobacteria has reached 92.8%.
Embodiment 8
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.002mol zinc nitrate and 0.001mol cobalt nitrate is added, mole
Than for 2:1, and 0.25g neopelex is added as surfactant, stirring to powder is uniformly dissolved, and forms solution
B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
S2, ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, with de-
Rouge cotton rub is done spare；
Colloidal sol is poured into ultrasonic spray pyrolysis device, places ceramics on the heating by pretreated ceramic tile print
In base substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 45min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 3cm
It plates to be put into baking oven after a tunic and dry in journey and plates within 30-60 minute the second layer again, all plate drying 5-10 hours afterwards.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 600 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
To embodiment 8 prepare cobalt/zinc doping TiO 2 sol nano material carry out XRD, SEM, UV-Vis-DRS,
The test such as FT-IR, each test result difference is as shown in figs. 12-15.Embodiment 8 is prepared into cobalt/zinc doping by sol-gel method
The nano material of TiO 2 sol is tested by the antibacterial around-France anti-microbial property to Escherichia coli, and test result is as follows schemes
Shown in 16.
In conjunction with Figure 12-15, make a concrete analysis of as follows: Figure 12 is XRD points of cobalt/zinc doping TiO 2 sol nano material
Analysis figure.As figure shows, there is TiO in 2 θ=27 ° or so2Anatase highest peak, the main object of the nano material is mutually Detitanium-ore-type
TiO2, also with a small amount of rutile TiO2Generate, be formed simultaneously the CoTiO of doping type3、Zn2Ti3O3And CO3O4.Thus may be used
See, the doping of Co/Zn ion increases TiO2The object phase composition of nano material.Figure 13 is cobalt/zinc doping TiO 2 sol
The sem analysis figure of nano material.Such as figure, there are many fine particles and aggregate to form for the nano material, and particle doping is close equal
Even, particle is tiny, and for shape in spherical, agglomeration is preferable.Figure 14 is cobalt/zinc doping TiO 2 sol nano material
UV-Vis-DRS analysis chart.Co/Zn adulterates TiO2Nano material has expanded absorption spectrum, makes absorption band red shift, in visible light model
There is higher absorbance in enclosing, significantly improves photocatalysis TiO2To the responding ability of visible light.It, can after this illustrates doping Co/Zn
Make TiO2Red shift occurs for ABSORPTION EDGE, causes TiO2Band gap narrow, more carriers can be generated under visible light action, thus
Improve TiO2Optical response range.Figure 15 is the FT-IR map of cobalt/zinc doping TiO 2 sol nano material.As schemed
Show there is a Ti-O stretching vibration peak at 531.02nm, there is a C-O-C stretching vibration peak, 1631.24 Hes at 1396.68
There is O-H stretching vibration peak at 3430.27, material surface hydroxyl is more, nano-TiO2Photocatalytic activity it is higher, produced in the material
Raw O-H stretching vibration peak is conducive to generate more hydroxyl free radicals, improves light-catalyzed reaction activity.This is because nanometer
TiO2There are titanium hydroxyl structures on surface, and titanium hydroxyl is the shallow potential well for capturing photohole, and can react produces peroxide,
Rise effectively prevent it is compound.Therefore surface hydroxyl is more, nano-TiO2Photocatalytic activity it is higher.
Figure 16 is the antibacterial ring size figure of cobalt/zinc doping TiO 2 sol nano material.There is figure can be seen that, around sample
There is Clear & Transparent antibacterial ring size, anti-microbial property is good.Zinc nitrate and cobalt nitrate molar ratio are the nano material of 2:1 to big
The sterilizing rate of enterobacteria has reached 96.4%.
Embodiment 9
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.02mol lithium acetate and 0.004mol zinc nitrate is added, mole
Than for 5:1, and 0.25g neopelex (SDBS) is added as surfactant, stirring to powder is uniformly dissolved, shape
At solution B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
S2, ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, with de-
Rouge cotton rub is done spare；
Colloidal sol is poured into ultrasonic spray pyrolysis device, places ceramics on the heating by pretreated ceramic tile print
In base substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 45min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 3cm
It plates to be put into baking oven after a tunic and dry in journey and plates within 30-60 minute the second layer again, all plate drying 5-10 hours afterwards.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 600 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
Embodiment 10-13
The step of with embodiment 9, is similar, embodiment 10-13 be only the kinds of surfactants in set-up procedure S1 come it is real
Existing, remaining condition is constant.Specifically, the kinds of surfactants in embodiment 10,11,12,13 is respectively dodecyl sulphate
Sodium (SDS), dodecyl sodium sulfate (SLS), Polyethylene glycol-2000 (PET2000) and cetyl trimethylammonium bromide
(CTAB)。
9-13 in conjunction with the embodiments passes through oscillation to the nano material of the cobalt doped TiO 2 sol of embodiment 9-13 preparation
Flask method and the antibacterial around-France anti-microbial property to Escherichia coli are tested, test result is as follows Figure 17, shown in 18.Figure 17 is not
Cobalt doped titanium dioxide nano material with surfactant influences the anti-microbial property of Escherichia coli.It can be seen that be added yin from
The cobalt doped TiO 2 sol nano material anti-microbial property of sub- surfactant SDS, SLS and SDBS is higher than other two kinds of doping
Surfactant.This may be the TiO due in aqueous solution2Surface potential is positive, and cationic and nonionic agent are opposite
It is difficult to be adsorbed onto catalyst surface, therefore the activity of reaction can be reduced.And under suitable conditions, anionic surfactant
It is readily adsorbed in TiO2Surface promotes light-catalyzed reaction to carry out.It is the cobalt doped titanium dioxide of different surfaces activating agent from Figure 18
The antibacterial ring size figure of the nano material of colloidal sol., it is apparent that neopelex (SDBS), lauryl sodium sulfate
(SDS), sample week of the dodecyl sodium sulfate (SLS) as the nano material of the cobalt doped TiO 2 sol of surfactant
Existing very Clear & Transparent antibacterial ring size is crossed, inhibition zone diameter has respectively reached 35mm, 36mm, 37mm.Polyethylene glycol-2000
(PET2000) and nanometer of the cetyl trimethylammonium bromide (CTAB) as the cobalt doped TiO 2 sol of surfactant
Antibacterial ring size around the sample of material is very small, and diameter is almost 0.
Embodiment 14
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.001mol cobalt nitrate is added, and 0.25g dodecyl is added
Benzene sulfonic acid sodium salt is uniformly dissolved as surfactant, stirring to powder, forms solution B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
S2, ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, with de-
Rouge cotton rub is done spare；
Colloidal sol is poured into ultrasonic spray pyrolysis device, places ceramics on the heating by pretreated ceramic tile print
In base substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 45min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 3cm
It plates to be put into baking oven after a tunic and dry in journey and plates within 30-60 minute the second layer again, all plate drying 5-10 hours afterwards.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 600 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
Embodiment 15-18
The step of with embodiment 14, is similar, and embodiment 15-18 is that only plated film height in set-up procedure S2 is realized, remaining
Condition is constant.Specifically, the plated film height in embodiment 15,16,17,18 is respectively 5cm, 8cm, 10cm, 12cm.
14-18 in conjunction with the embodiments is logical to the anti-bacteria ceramic of the cobalt doped titanium dioxide nano material of embodiment 14-18 preparation
It crosses oscillation flask method to test the anti-microbial property of Escherichia coli, test result is as shown in figure 19.Plating to optimal antibiotic rate
Film height example 16 carries out XRD, SEM test, and each test result is respectively as shown in Figure 20,21.Figure 19 is different plated film height
Cobalt doped titanium dioxide nano material anti-bacteria ceramic influences the anti-microbial property of Escherichia coli.As seen from the figure, plated film height is 8cm
When cobalt doped titanium dioxide nano material anti-bacteria ceramic it is best to the bactericidal effect of Escherichia coli, reached 55% or more, it
Afterwards as the increase antibiotic rate of plated film height reduces.Therefore plated film height selects 8cm in subsequent experimental, sprays under the height more
Even, antibacterial effect is more preferable.The XRD spectrum of Figure 20 is plated film height anti-bacteria ceramic prepared when being 8cm.Due to titanium dioxide
Antibacterial film with a thickness of nanoscale, when doing X-ray diffraction, X-ray breaks through nano thin-film and directly beats in ceramic tile print
On, the peak for causing the strong peak in the XRD spectrum made to go out for object phase institute's diffraction of ceramic tile print, titanium dioxide antibiotic film is spread out
The peak of injection is all some very weak peaks.It is seen that in addition to the composition SiO2 of ceramics itself, on ceramic tile print also
TiO2、CoTi2, the multi-component materials such as Co2Ti, keeping nano-TiO2On the basis of generate CoTi2And Co2Ti doping type object
Matter.The SEM spectrum of Figure 21 is plated film height anti-bacteria ceramic prepared when being 8cm.It can be seen from the figure that super using self-control
The anti-bacteria ceramic film forming for the cobalt doped titanium dioxide nano material that sound spraying device is prepared when plated film height is 8cm is uniform,
The smooth densification of film surface, the anti-bacteria ceramic of cobalt doped titanium dioxide nano material substrate surface without or few agglomeration, film exist
The attachment of base surface is close, not easily to fall off.There is a small amount of crackle on film, this may be in the process with ultrasonic spray pyrolysis plated film
The temperature of middle ceramic bases liner is excessively high, and the intermolecular stress for the sol particles being sprayed on ceramic tile print is caused to increase, thus
Crackle is produced, but this crackle does not influence antibacterial effect.
Embodiment 19
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.001mol cobalt nitrate is added, and 0.25g dodecyl is added
Benzene sulfonic acid sodium salt is uniformly dissolved as surfactant, stirring to powder, forms solution B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
Ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, uses degreasing
Cotton rub is done spare.
S2, colloidal sol is poured into ultrasonic spray pyrolysis device, is placed on the heating by pretreated ceramic tile print
On ceramic substrate substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 45min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 8cm
A tunic is plated in journey, drying 5-10 hours after all having plated.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 600 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
Embodiment 20-21
The step of with embodiment 19, is similar, and embodiment 20,21 is that only coating layers in set-up procedure S2 are realized, remaining
Condition is constant.Specifically, the coating layers in embodiment 20,21 are respectively 2 layers, 3 layers.
19-21 in conjunction with the embodiments is logical to the anti-bacteria ceramic of the cobalt doped titanium dioxide nano material of embodiment 19-21 preparation
It crosses oscillation flask method to test the anti-microbial property of Escherichia coli, test result is as shown in figure 22, and to optimal antibiotic rate
Coating layers example 20 carries out XRD, SEM test, and each test result is respectively as shown in Figure 23,24.Figure 22 is different coating layers
Cobalt doped titanium dioxide nano material anti-bacteria ceramic the anti-microbial properties of Escherichia coli is influenced.As seen from the figure, coating layers 2
Antibiotic rate highest when layer, antibiotic rate only has 41% when coating layers are one layer, and when coating layers increase to three layers, antibiotic rate drop
As low as 35%, antibacterial effect is unobvious.The XRD spectrum of Figure 23 is coating layers anti-bacteria ceramic prepared when being 2 layers.Such as
Shown in figure, in addition to the component SiO2 of ceramic tile print itself, the constituent of film mutually has TiO on print2、CoTi2O3And Co2Ti2O,
Cobalt doped titanium dioxide nano material colloidal sol maintains original object phase composition after plated film.With Figure 20 coating be one layer when spread out
It penetrates peak to compare, TiO when coating is two layers2And its doping particle diffraction maximum enhanced, show coating be two layers be ceramic tile sample
The antimicrobial levels of on piece increased.The SEM spectrum of Figure 24 is coating layers anti-bacteria ceramic prepared when being 2 layers.From
As can be seen that being 8cm in plated film height in figure, the cobalt doped titanium dioxide nano material that coating layers are prepared when being two layers
Anti-bacteria ceramic film is uniform.It can be seen that film when coating layers are two layers compared with SEM figure when coating layers in Figure 21 are one layer
General thickness increase, agglomeration is few, but many tiny crackles occurs, it can be seen that these crackles be the second layer plating
The crackle of film.This may be or even to penetrate into inside ceramic tile because first layer plated film is close to ceramic tile surface, with ceramic tile attachment compared with
It is good, and more evenly securely, and second layer plated film is in the completely dry later progress of first layer plated film gel, adhesive force is poor to lead
Cause many crackles.And coating has many tiny colloidal sol little particles to be attached to when being two layers be shakiness due to device above
It is qualitative that few sol particle is caused not filter in surge chamber and arrived spraying area, it has been attached to ceramic tile surface.
Embodiment 22
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.001mol cobalt nitrate is added, and 0.25g dodecyl is added
Benzene sulfonic acid sodium salt is uniformly dissolved as surfactant, stirring to powder, forms solution B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
S2, ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, with de-
Rouge cotton rub is done spare；
Colloidal sol is poured into ultrasonic spray pyrolysis device, places ceramics on the heating by pretreated ceramic tile print
In base substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 30min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 8cm
It plates to be put into baking oven after a tunic and dry in journey and plates within 30-60 minute the second layer again, all plate drying 5-10 hours afterwards.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 600 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
Embodiment 23-25
The step of with embodiment 22, is similar, and embodiment 23-25 is that only plated film time length in set-up procedure S2 is realized,
Remaining condition is constant.Specifically, the plated film time length in embodiment 23-25 is respectively 45min, 60min, 75min.
22-25 in conjunction with the embodiments is logical to the anti-bacteria ceramic of the cobalt doped titanium dioxide nano material of embodiment 22-25 preparation
It crosses oscillation flask method to test the anti-microbial property of Escherichia coli, test result is as shown in figure 25, and to optimal antibiotic rate
Plated film time example 23 carries out XRD, SEM test, and each test result is respectively as shown in Figure 26,27.Figure 25 is different plated film times
Cobalt doped titanium dioxide nano material anti-bacteria ceramic the anti-microbial properties of Escherichia coli is influenced.As seen from the figure, plated film time is
The anti-bacteria ceramic of cobalt doped titanium dioxide nano material is best to the bactericidal effect of Escherichia coli when 45min.Plated film time is
The anti-bacteria ceramic sterilizing rate of prepared cobalt doped titanium dioxide nano material has reached 92% or more when 45min, when plated film
Between not enough or overlong time can all influence antibacterial effect.Figure 26 is plated film time anti-bacteria ceramic prepared when being 45min
XRD spectrum.As seen from the figure, in addition to the component SiO of ceramics itself2、CaCO3With antibacterial agent TiO2Outside, Ti3SiC is also generated2。
Ti3SiC2It is the Typical Representative of novel processable ceramics material MAX phase.Many excellent performances of this kind of material collection metal and ceramics
, there is good electric conductivity, thermal conductivity and machinability as metal material；Also have ceramic material good resistance to
Corrosivity, inoxidizability and high-temperature stability.This substance may be because of TiO2Colloidal sol has penetrated into ceramic inside, in high temperature
TiO during roasting2With SiO2What reaction generated.Figure 27 is plated film time anti-bacteria ceramic prepared when being 45min
SEM spectrum.It can be seen from the figure that the anti-bacteria ceramic for the cobalt doped titanium dioxide nano material prepared with this condition forms a film
Uniformly, adhere between film and substrate close.As can be seen that Ceramic Like compared with SEM figure when plated film time in Figure 24 is 30min
On piece still has a small amount of TiO2Aggregate, but plated film time be 45min when film it is more thick and solid, cracking phenomena significantly reduces.Plated film
When time is 45min, there are some spileholes in film surface, this can be super because there is impurity to enter self-control in coating process
Sound spraying system, so that impurity is coated in ceramic tile surface with colloidal sol, impurity is mingled in TiO2In film, ceramic tile print is in horse
The not heated volatilization of impurity during furnace high-temperature roasting, to leave some small stomatas in film surface, these stomatas are simultaneously
It will not influence the anti-microbial property of ceramic tile print.
Embodiment 26
S1,10mL butyl titanate is measured at room temperature in pyriform funnel, be slowly added in 70mL dehydrated alcohol, stir
30min is uniformly mixed, and forms solution A；
4mL glacial acetic acid is added in 70mL dehydrated alcohol, 0.001mol cobalt nitrate is added, and 0.25g dodecyl is added
Benzene sulfonic acid sodium salt is uniformly dissolved as surfactant, stirring to powder, forms solution B；
Solution A is slowly titrated and is added in solution B, 30min is stirred after being added dropwise and obtains colloidal sol.
S2, ceramic tile is put into deionized water, dehydrated alcohol, respectively cleans 30min in ultrasonic cleaner in acetone, with de-
Rouge cotton rub is done spare；
Colloidal sol is poured into ultrasonic spray pyrolysis device, places ceramics on the heating by pretreated ceramic tile print
In base substrate, underlayer temperature is controlled at 60 DEG C or so；
Spraying plated film 45min, plated film mistake under conditions of plated film height (i.e. height of the ceramic tile print apart from nozzle) is 8cm
It plates to be put into baking oven after a tunic and dry in journey and plates within 30-60 minute the second layer again, all plate drying 5-10 hours afterwards.
S3, the ceramic tile after drying is put into Muffle furnace be warming up to 400 DEG C from room temperature with the speed of 4 DEG C/min after keep the temperature
Two hours are roasted, anti-bacteria ceramic is made.
Embodiment 27-30
The step of with embodiment 26, is similar, and embodiment 27-30 is that only maturing temperature in set-up procedure S3 is realized, remaining
Condition is constant.Specifically, the maturing temperature in embodiment 27-30 is respectively 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C.
26-30 in conjunction with the embodiments carries out the nano material of the cobalt doped TiO 2 sol of embodiment 26-30 preparation
XRD, SEM test, test result is respectively as shown in Figure 28,29.Cobalt doped nano titania material prepared by embodiment 26-30
The anti-bacteria ceramic of material tests the anti-microbial property of Escherichia coli by vibrating flask method, and test result is as follows shown in Figure 30.
In conjunction with Figure 28-30, make a concrete analysis of as follows: Figure 28 a-e be shown maturing temperature for 400 DEG C, 500 DEG C, 600 DEG C,
The XRD spectrum of cobalt doped titanium dioxide nano material anti-bacteria ceramic at 700 DEG C, 800 DEG C.As seen from the figure, maturing temperature 500
DEG C, 600 DEG C, 700 DEG C when TiO2Peak it is stronger, this is consistent with the result of antibacterial experiment.Object at each temperature is mutually in addition to ceramics
The SiO2 and TiO of itself2Outer all Co-Ti compound phases containing doping type.Film object when maturing temperature is 500~700 DEG C
Mutually it is not much different.TiO when maturing temperature is 400 DEG C and 800 DEG C2With doping type TiO2Peak obviously weaken, this is because 400 DEG C
When maturing temperature do not reach TiO2Transformation of crystal temperature, TiO2It is main or exist in the form of after colloidal sol is dried, with ceramic tile
Substrate engaging portion is close, is easy to fall off.And the TiO when maturing temperature is 800 DEG C2Mainly exist with Rutile Type, rutile
Photocatalytic activity be lower than anatase, this is consistent with the result of antibacterial experiment.
Figure 29 a-e is cobalt doped titanium dioxide nano material antibacterial when being 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C
The SEM spectrum of ceramics.It can be seen from the figure that the anti-bacteria ceramic that ultrasonic spray pyrolysis is prepared is under different maturing temperatures
Film-formation result it is different, as the temperature rises, film gradually becomes even compact, and maturing temperature is 500 DEG C, 600 DEG C and 700 DEG C
When film-formation result it is best, but maturing temperature is further continued for increasing, and film starts many cracking phenomenas occur.Occur on film at 800 DEG C
Many crackles, and there are many reunion glomerations on cobalt doped titanium dioxide nano material anti-bacteria ceramic surface, particle is larger.Thus may be used
To find out, the too high or too low film-formation result of maturing temperature is all bad, can all make cobalt doped titanium dioxide nano material anti-bacteria ceramic
Photocatalytic activity reduce.Its reason may be TiO during roasting2Crystal form converted, do not have when temperature is too low
Have and reaches TiO2The condition of transformation of crystal, TiO2Mainly exist with the very low rutile-type crystal of photocatalytic activity, when temperature reaches
TiO when certain temperature2It is converted into and exists with the high anatase crystal of photocatalytic activity, make between different crystal forms when the temperature is excessively high
Chemical bond rupture, film can also show cracking phenomena, so that the adhesive force of film be made to decline, influence the antibiotic property of anti-bacteria ceramic
Energy.
Figure 30 is the cobalt doped titanium dioxide nano material anti-bacteria ceramic of different maturing temperatures to Escherichia coli anti-microbial property
It influences, as seen from the figure, cobalt doped titanium dioxide nano material anti-bacteria ceramic is to large intestine bar when maturing temperature is 700 DEG C and 500 DEG C
The bactericidal effect of bacterium is best.
It is cleaned up in conclusion the antibacterial colloidal sol prepared is sprayed on by the present invention by homemade ultrasonic spray apparatus
Unglazed ceramic tile surface, high-temperature roasting makes its stabilisation in Muffle furnace after drying is dry.It is systematic to have studied metal
The titanium dioxide nano material colloidal sol of ion doping during the preparation process doping and doping molar ratio, the kind of surfactant
Plated film height, coating layers, plated film time and maturing temperature in class, anti-bacteria ceramic preparation process is to anti-bacteria ceramic antibiotic property
The influence of energy, probes into its best preparation process.Using Escherichia coli (ATCC 25922), golden yellow color staphylococcus (ATCC
6538) and Candida albicans (ATCC 10231) is used as experimental strain, using shake-flask method and antibacterial around-France studies metal
The anti-microbial property of ions doped titanium dioxide nano material, and utilize the means of testing pair such as XRD, SEM, UV-Vis-DRS, FT-IR
Anti-biotic material carries out performance characterization；The anti-microbial property of anti-bacteria ceramic is studied using film adhesion method, and is visited using XRD and SEM
Study carefully anti-bacteria ceramic surface film, performance characterization prepares the method phase of anti-bacteria ceramic with existing metal ion doped titanium dioxide
Comparison, supersonic spraying of the invention prepare metallic ion doped nano material anti-bacteria ceramic, nothing very big to the material scope of application
Whisker material is conductive, and operation equipment cost is lower, which is industrial ultrasonic atomizer, easy industrialization promotion,
Suitable material range is wide.Granularity fine and even after atomization, after surge chamber, larger atomized drop is stayed in surge chamber, mist
Change fine particle and enter spray equipment with air pump gas, since atomizing particle is subtle, easily penetrates into potsherd, potsherd table
The spraying in face is more evenly secured, and the later period is impregnated by sewage and the detection modes such as rain drop erosion carry out the fastness of its plated film
It examines.
It is to be appreciated that describing the skill simply to illustrate that of the invention to what specific embodiments of the present invention carried out above
Art route and feature, its object is to allow those skilled in the art to can understand the content of the present invention and implement it accordingly, but
The present invention is not limited to above-mentioned particular implementations.All various changes made within the scope of the claims are repaired
Decorations, should be covered by the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of plated film anti-bacteria ceramic, which comprises the following steps:
S1, it prepares doping vario-property colloidal sol: soluble titanium hydrochlorate, surfactant, at least one being added in a solvent for adulterating
Metal ion compound, under chelating agent existence condition, be made doping vario-property colloidal sol；
S2, the doping vario-property colloidal sol is sprayed into ceramic surface: using supersonic spraying, doping vario-property prepared by step S1
Colloidal sol sprays to ceramic surface, forms the doping vario-property sol pellicle of even compact；By the ceramic surface temperature control when spraying
System is at 50~70 DEG C；
The surface: being covered with the ceramics of doping vario-property sol pellicle by S3, calcination process, at high temperature aerobic roasting, and plating is made
There is metallic ion-doping modification TiO2The anti-bacteria ceramic of film.
2. the preparation method of plated film anti-bacteria ceramic according to claim 1, which is characterized in that step S1 step is added solvable
Property titanate be butyl titanate.
3. the preparation method of plated film anti-bacteria ceramic according to claim 1, which is characterized in that step S1 be added metal from
Sub- compound is at least one of lithium acetate, zinc nitrate, cobalt nitrate.
4. the preparation method of plated film anti-bacteria ceramic according to claim 1, which is characterized in that the surface that step S1 is added is living
Property agent be neopelex, lauryl sodium sulfate, dodecyl sodium sulfate, Polyethylene glycol-2000 and cetyl
One of trimethylammonium bromide.
5. the preparation method of plated film anti-bacteria ceramic according to claim 1, which is characterized in that doping vario-property is made in step S1
Titanate in colloidal sol, dehydrated alcohol, glacial acetic acid and water volume ratio be 1:14:4:1.
6. a kind of preparation method of plated film anti-bacteria ceramic according to claim 1, which is characterized in that step S2 is mixed described
Plated film height is 3cm-15cm when miscellaneous modification sol sprays to ceramic surface, every layer of plated film time is 30-90min, coating layers
It is 1-4 layers.
7. a kind of preparation method of plated film anti-bacteria ceramic according to claim 6, which is characterized in that step S2 plated film twice
Between ceramics to dry 30-60min, 5-10 hours drying temperatures of drying are 90~105 DEG C after all plate, drying time 12
~for 24 hours.
8. the preparation method of plated film anti-bacteria ceramic according to claim 1, which is characterized in that dried when step S3 calcination process
After roasting temperature is warming up to 400-800 DEG C with the rate of 4 DEG C/min from room temperature, heat preservation roasting 1-5 hours.
9. a kind of preparation method of the preparation method plated film anti-bacteria ceramic of plated film anti-bacteria ceramic according to claim 1,
It is characterized in that, potsherd used in step S2 is the conventional ceramic piece for not plating glaze paint, and super with deionized water, dehydrated alcohol and acetone
Sound cleans 2 hours.
10. a kind of plated film anti-bacteria ceramic, which is characterized in that be made according to the described in any item preparation methods of claim 1-9.
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| CN112645740A (en) * | 2020-12-23 | 2021-04-13 | 常州北化澳联环保科技有限公司 | Preparation method of anti-skid antibacterial ceramic tile |
| CN112898001A (en) * | 2021-02-03 | 2021-06-04 | 福建省德化县卓越陶瓷有限公司 | Negative ion antibacterial white porcelain and preparation method thereof |
| CN113061055A (en) * | 2021-03-25 | 2021-07-02 | 景德镇陶瓷大学 | Antibacterial ceramic product and preparation method and application thereof |
| CN113829767A (en) * | 2021-09-23 | 2021-12-24 | 佛山市南海区金之岚装饰材料有限公司 | Production process of mosaic ceramic tile imitating wood grains and stone grains |
| CN115636694A (en) * | 2022-12-26 | 2023-01-24 | 佛山市陶莹新型材料有限公司 | Nano self-cleaning ceramic glaze and preparation method thereof |
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| CN112645740A (en) * | 2020-12-23 | 2021-04-13 | 常州北化澳联环保科技有限公司 | Preparation method of anti-skid antibacterial ceramic tile |
| CN112898001A (en) * | 2021-02-03 | 2021-06-04 | 福建省德化县卓越陶瓷有限公司 | Negative ion antibacterial white porcelain and preparation method thereof |
| CN113061055A (en) * | 2021-03-25 | 2021-07-02 | 景德镇陶瓷大学 | Antibacterial ceramic product and preparation method and application thereof |
| CN113829767A (en) * | 2021-09-23 | 2021-12-24 | 佛山市南海区金之岚装饰材料有限公司 | Production process of mosaic ceramic tile imitating wood grains and stone grains |
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Application publication date: 20190129 |